EP0460138A1 - Procede de fabrication de chloroforme - Google Patents

Procede de fabrication de chloroforme Download PDF

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Publication number
EP0460138A1
EP0460138A1 EP91900030A EP91900030A EP0460138A1 EP 0460138 A1 EP0460138 A1 EP 0460138A1 EP 91900030 A EP91900030 A EP 91900030A EP 91900030 A EP91900030 A EP 91900030A EP 0460138 A1 EP0460138 A1 EP 0460138A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
palladium
hydrogen
metal
foregoing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91900030A
Other languages
German (de)
English (en)
Other versions
EP0460138B1 (fr
Inventor
Emilio Tijero Miquel
José Maria SULE GIMENEZ
Antonio Cortes Arroyo
Xose Lois Seoane Gomez
Adolfo Arcoya Martin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ercros SA
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Ercros SA
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Filing date
Publication date
Application filed by Ercros SA filed Critical Ercros SA
Publication of EP0460138A1 publication Critical patent/EP0460138A1/fr
Application granted granted Critical
Publication of EP0460138B1 publication Critical patent/EP0460138B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • C07C19/03—Chloromethanes
    • C07C19/04—Chloroform
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a process for the preparation of chloroform (CHCl3), starting out from carbon tetrachloride (CCl4).
  • liquid phase carbon tetrachloride is reacted with hydrogen gas or with a molecular hydrogen-containing gas, in the presence of a catalyst based on a metal selected from the group formed by palladium, rhodium, ruthenium and platinum, said catalyst being contained in suspension in the liquid.
  • the reaction is conducted in liquid phase, with a supported powdered metal catalyst in suspension in contact with the molecular hydrogen.
  • the catalyst active component is a metal selected from the group formed by palladium, rhodium, ruthenium and platinum.
  • the process has proved to be particularly effective when the chosen metal is palladium.
  • a further important advantage of the process of the invention is that it allows the temperature to be easily controlled, thereby avoiding the formation of chlorinated polymers and it also allows the activity of the catalyst to be maintained for sufficient time to make the process commercially profitable.
  • the catalyst used in the process of the invention is formed by a metal selected from the group formed by palladium, rhodium, ruthenium and platinum deposited on a suitable substrate, such as carbon, silica, alumina, etc.
  • a catalyst having shown itself to have a high activity and selectivity together with high stability is metallic palladium deposited on activated carbon having a large surface area.
  • the metal may be deposited on the substrate by any of the methods regularly used for this purpose, such as, for example, impregnation with or without an excess of solution, precipitation, etc, using aqueous or organic solvents.
  • chlorides As precursor salts of the metal, chlorides, ammoniacal chlorides, organic complexes, nitrates, acetates, etc. may be used, both in the commercial form thereof and as a result of dissolving the metal in an appropriate solvent.
  • the precursor Once the precursor has been deposited on the substrate, it is allowed to dry at room temperature for three hours and subsequently at a temperature ranging from 100 o C to 140 o C for the time required to remove the residual water.
  • the catalyst is reduced to the metallic state in the presence of a molecular hydrogen-containing gas or an appropriate reducing gas such as hydrazine, methane, etc.
  • a molecular hydrogen-containing gas or an appropriate reducing gas such as hydrazine, methane, etc.
  • the reduction may be effected at temperatures ranging from 100 o C to 500 o C, preferably from 150 o C to 450 o C, the range of 200 o C to 300 o C being most advantageous when the metal is palladium.
  • the reduction may be effected at atmospheric pressure or at a higher pressure.
  • the optimum duration ranges from 1 to 4 hours and the hydrogen flow from 200 to 1,000 litres/hour per kg of catalyst, although an amount of hydrogen ranging from 2 to 5 times the amount required to reduce all the metal is sufficient.
  • the metal content of the catalyst may range from 0.1 to 5 wt% relative to the total weight of the final catalyst, although the preferred range is from 0.1 to 2 wt%.
  • a high solid-liquid contact area is required, whereby it is desirable to use the catalyst in powder form, with a particle size not above 0.45 mm and preferably of less than 0.2 mm.
  • any conventional mechanical stirring system may be used, or advantage may be taken of the linear velocity of the hydrogen itself, adequately dispersed in the liquid, to create the necessary turbulence.
  • the substrate may initially have the form of pellets, grains or extrudates, to be subsequently reduced to the selected particle size. Nevertheless, the metal precursor may also be incorporated directly on the powdered substrate.
  • this new process of manufacturing chloroform by catalytic hydrogenolysis of carbon tetrachloride is characterized essentially in being conducted in the liquid phase, containing the appropriate amount of powdered catalyst in suspension, in the presence of hydrogen at an appropriate temperature and pressure.
  • the process may be operated indifferently batchwise, semi-continuously or continuously.
  • a stirred autoclave type reactor may be used, containing the liquid carbon tetrachloride and catalyst charge, in the appropriate proportions. Hydrogen is allowed to flow in up to the set pressure, the mass is heated up to the operating temperature and is held under these conditions for the time required to achieve the desired conversion. At the end of this time, the reaction products are discharged and separated. Both the unreacted reactant and the catalyst may be reused.
  • either an autoclave type reactor or a tubular reactor may be used.
  • the liquid and the catalyst are charged in the required proportions and the required hydrogen flow is provided.
  • the working temperature and pressure are adjusted.
  • the gaseous effluent of the reactor containing H2, hydrogen chloride, methane and chlorinated hydrocarbons, is fed through a water absorption column where the hydrogen chloride is retained. Thereafter, the chlorinated products are condensed at a desirable temperature and the main reaction product, i.e. the chloroform is separated from them, for example, by distillation. If necessary, the gas flow and the unreacted reactant may be recycled.
  • the apparatus is provided with a cyclone and/or filter to recover any entrained catalyst and return it to the reactor.
  • the observed losses of catalyst are minimal.
  • the reactor content after removal of the catalyst, is sent to distillation to recover the chloroform.
  • the unreacted carbon tetrachloride is recycled to the reactor.
  • the process may be carried out equally well reversing the order described above for the chlorinated product condensation and the hydrogen chloride absorption. This last operating method is more appropriate for application in an industrial plant.
  • the same operating method is used as in the above described semi-continuous method, except that in this case the carbon tetrachloride is also supplied continuously in liquid phase at the required flow rate.
  • the two reactor effluents, gas and liquid, are separated and processed as in the previously described semi-continuous operation.
  • the high activity shown by the catalyst used in the process of the invention, together with the reaction being carried out in the liquid phase, not only allows low temperatures to be used, but also an excellent control of the temperature within the reactor to be maintained, the gradients not normally exceeding the values of T ⁇ 5 o C.
  • the reaction may be carried out with satisfactory yields at temperatures ranging from 100 o C to 300 o C, although temperatures ranging from 120 o C to 160 o C are preferable.
  • the reaction is conducted advantageously at pressures above atmospheric pressure. Excessively high pressures do not provide substantial advantages to the reaction kinetics and increase the production costs. Therefore, the operating pressure should range from 500 to 8,000 kpa and preferably from 1,500 to 5,000 kpa.
  • the hydrogen supply should be sufficient selectively to produce the desired reaction, i.e. the preparation of chloroform.
  • This reaction is: CCl4 + H2 ⁇ CHCl3 + HCl
  • Another parameter determining the commercial profitability of this process is the relatively low content of metal used as active component, both in the catalyst composition and in the catalyst/chlorinated reactant (wt/wt) ratio used in the reactor.
  • the productivity increases more than linearly on increasing it, since thereby the amount of catalyst particles in the slurry and, therefore, the contact area of the catalyst, also increase.
  • the reaction rate is proportional to this area. Nevertheless, for higher values, competition occurs for the H2 among the catalyst particles, whereby there is a reduction of the effective amount of catalyst, saturation is reached and the activity per gram practically no longer increases.
  • ratios ranging from 0.1/100 and 5/100 (wt/wt), more preferably 0.5/100 to 2.5/100, have been found to be acceptable for the catalyst/CCl4 ratio.
  • the highest rates of chloroform production, expressed as kg CHCl3/hour per kg palladium are obtained with these ratios.
  • This Example relates to a way of preparing a palladium catalyst, using activated carbon of 1,200 m2/g as substrate, in the form of pellets of about 3 mm diameter by 4 mm long.
  • the retention volume or maximum water absorption volume is 95 cm3/g.
  • the pellets were thoroughly stirred to produce a homogenous absorption of the solution, it was allowed to dry at room temperature for three hours and then at 120 o C for twelve hours. Subsequently, it was reduced at 250 o C at atmospheric pressure, with 500 l/hour hydrogen per kg catalyst being blown over for three hours. It was allowed to cool to room temperature under hydrogen flow.
  • the catalyst contained 1 wt% of palladium metal.
  • the catalyst pellets were reduced to a size of below 0.177 mm.
  • This Example relates to the preparation of chloroform (CHCl3).
  • the selectivity (S) is defined as the number of moles of carbon tetrachloride converted into product, divided by the total number of moles of carbon tetrachloride reacted multiplied by 100.
  • the main by-products obtained were:
  • the complements to 100 of the selectivity sums correspond to small amounts of other by-products, such as ethane, trichloroethane, pentachloroethane and traces of others.
  • a palladium catalyst containing 1 wt% of metal was prepared, using as substrate a different activated carbon having a specific area of 820 m3/g and 78% retaining volume.
  • This Example relates to a way of preparing a rhodium (Rh) catalyst.
  • a rhodium (Rh) catalyst was prepared by dissolving in distilled water the amount of rhodium trichloride (RhCl3) necessary for the final catalyst to contain 1 ⁇ 6 wt% of rhodium metal relative to the total catalyst weight. Distilled water was added to the resulting solution to complete a volume equal to the retention volume of the carbon used in Example 1. After impregnating the substrate with this solution, it was dried at 120 o C for twelve hours and was then reduced at 150 o C, under flowing hydrogen, for two hours.
  • RhCl3 rhodium trichloride
  • This Example relates to a way of preparing a ruthenium (Ru) catalyst.
  • a catalyst containing 1 ⁇ 6 wt% of ruthenium (Ru) was prepared from ruthenium trichloride (RuCl3, using the same method and substrate as in Example 9, except that the reduction was conducted at 250 o C.
  • This Example relates to a way of preparing a platinum (Pt) catalyst.
  • a platinum catalyst was prepared using powdered silica of 600 m2/g specific area and 3 ⁇ 0 cm3/g specific retention volume as substrate. 1g of hexachloroplatinic acid (H2PtCl6.6H2O) was dissolved in distilled water to complete a volume of 113 cm3. The solution was poured over 37.5 g of substrate. Once the solid was well impregnated, it was dried at 120 o C for 12 hours, was calcined at 500 o C under flowing air for two hours and was reduced at 450 o C under flowing hydrogen for two hours. The final catalyst contained 1 wt% of platinum metal.
  • H2PtCl6.6H2O hexachloroplatinic acid
  • Example 15 also deals with the preparation of a platinum catalyst.
  • Example 13 Following the method of Example 13, a platinum catalyst was prepared, but using the activated carbon of Example 6. After impregnation and drying, the catalyst was reduced directly with H2 at 450 o C, without prior calcination. The final catalyst contained 1 wt% of platinum metal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Steroid Compounds (AREA)

Abstract

Procédé de fabrication de chloroforme par hydrogénolyse catalytique de tétrachlorure de carbone en phase liquide, caractérisé en ce que l'on fait réagir du tétrachlorure de carbone en phase liquide avec de l'hydrogène gazeux ou avec un gaz contenant de l'hydrogène moléculaire, à une pression inférieure à 8000 kPa et à une température inférieure à 250 °C, en présence d'un catalyseur constitué par un métal sélectionné dans le groupe comprenant le palladium, le rhodium, le ruthénium et le platine, deposé sur un substrat, pulvérisé et maintenu en suspension dans le liquide. Ce procédé s'applique à la production industrielle de chloroforme à partir de tétrachlorure de carbone.
EP91900030A 1989-12-22 1990-12-13 Procede de fabrication de chloroforme Expired - Lifetime EP0460138B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ES8904342A ES2018748A6 (es) 1989-12-22 1989-12-22 Procedimiento para la fabricacion de cloroformo.
ES8904342 1989-12-22
PCT/ES1990/000047 WO1991009827A1 (fr) 1989-12-22 1990-12-13 Procede de fabrication de chloroforme

Publications (2)

Publication Number Publication Date
EP0460138A1 true EP0460138A1 (fr) 1991-12-11
EP0460138B1 EP0460138B1 (fr) 1995-02-15

Family

ID=8265208

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91900030A Expired - Lifetime EP0460138B1 (fr) 1989-12-22 1990-12-13 Procede de fabrication de chloroforme

Country Status (11)

Country Link
US (1) US5208393A (fr)
EP (1) EP0460138B1 (fr)
JP (1) JP2812800B2 (fr)
KR (1) KR0178540B1 (fr)
AT (1) ATE118473T1 (fr)
AU (1) AU642187B2 (fr)
BR (1) BR9007163A (fr)
CA (1) CA2046892C (fr)
DE (1) DE69017012T2 (fr)
ES (1) ES2018748A6 (fr)
WO (1) WO1991009827A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018447A1 (fr) * 1991-04-23 1992-10-29 Ag Technology Co., Ltd. Procede pour la production d'hydrochloromethanes
EP0652195A1 (fr) * 1993-11-04 1995-05-10 ENICHEM S.p.A. Préparation de CHCl3 à partir de CCl4
EP4321238A1 (fr) 2022-08-08 2024-02-14 Grillo-Werke Aktiengesellschaft Déhalogénation des hydrocarbures halogénés

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5621151A (en) * 1990-10-09 1997-04-15 E. I. Du Pont De Nemours And Company Halocarbon hydrogenolysis
KR100395208B1 (ko) * 2000-11-06 2003-08-21 학교법인 포항공과대학교 비균등화반응을 이용한 사염화탄소의 처리 방법
JP4519438B2 (ja) * 2003-10-08 2010-08-04 株式会社トクヤマ 多塩素化アルカンの還元用触媒
CN107876046A (zh) * 2017-10-27 2018-04-06 江苏理文化工有限公司 一种四氯化碳气相加氢脱氯制氯仿的高效催化剂
CN108147943A (zh) * 2018-01-19 2018-06-12 江苏理文化工有限公司 一种四氯化碳转氯仿生产工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579595A (en) * 1968-01-19 1971-05-18 Baxter Laboratories Inc 1-bromo-1-chloro-2,3,3-trifluoropropene and method of preparing same
US3579596A (en) * 1968-03-29 1971-05-18 Dow Chemical Co Hydrogenolysis of carbon tetrachloride and chloroform
GB1268518A (en) * 1968-10-12 1972-03-29 Sumitomo Chemical Co Method for production of methyl isobutyl ketone
IT965496B (it) * 1971-09-27 1974-01-31 Sumitomo Chemical Co Procedimento per la produzione di idrocarburi clorurati
FR2661671B1 (fr) * 1990-05-03 1992-07-17 Atochem Procede de dechloration des chloromethanes superieures.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9109827A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018447A1 (fr) * 1991-04-23 1992-10-29 Ag Technology Co., Ltd. Procede pour la production d'hydrochloromethanes
EP0652195A1 (fr) * 1993-11-04 1995-05-10 ENICHEM S.p.A. Préparation de CHCl3 à partir de CCl4
EP4321238A1 (fr) 2022-08-08 2024-02-14 Grillo-Werke Aktiengesellschaft Déhalogénation des hydrocarbures halogénés

Also Published As

Publication number Publication date
US5208393A (en) 1993-05-04
AU6891691A (en) 1991-07-24
CA2046892A1 (fr) 1991-06-23
CA2046892C (fr) 2001-08-07
KR920701091A (ko) 1992-08-11
EP0460138B1 (fr) 1995-02-15
WO1991009827A1 (fr) 1991-07-11
DE69017012D1 (de) 1995-03-23
BR9007163A (pt) 1992-03-03
ES2018748A6 (es) 1991-05-01
JP2812800B2 (ja) 1998-10-22
JPH04504728A (ja) 1992-08-20
AU642187B2 (en) 1993-10-14
DE69017012T2 (de) 1995-06-22
ATE118473T1 (de) 1995-03-15
KR0178540B1 (ko) 1999-05-15

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